EP3689636A1 - Reactive solvent-free adhesive composition and method of manufacturing tire using same - Google Patents
Reactive solvent-free adhesive composition and method of manufacturing tire using same Download PDFInfo
- Publication number
- EP3689636A1 EP3689636A1 EP19206621.5A EP19206621A EP3689636A1 EP 3689636 A1 EP3689636 A1 EP 3689636A1 EP 19206621 A EP19206621 A EP 19206621A EP 3689636 A1 EP3689636 A1 EP 3689636A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- adhesive composition
- rubber
- compound
- reactive solvent
- oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 76
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 76
- 239000000203 mixture Substances 0.000 title claims abstract description 69
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 229920005862 polyol Polymers 0.000 claims abstract description 36
- 150000003077 polyols Chemical class 0.000 claims abstract description 36
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 33
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 239000003999 initiator Substances 0.000 claims abstract description 22
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 20
- 239000004636 vulcanized rubber Substances 0.000 claims description 26
- -1 aliphatic thiol compound Chemical class 0.000 claims description 25
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 9
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims description 7
- 150000002978 peroxides Chemical class 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 claims description 3
- 229920003194 trans-1,4-polybutadiene polymer Polymers 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 description 39
- 238000004073 vulcanization Methods 0.000 description 39
- 239000005060 rubber Substances 0.000 description 37
- 239000003795 chemical substances by application Substances 0.000 description 22
- 229920005989 resin Polymers 0.000 description 22
- 239000011347 resin Substances 0.000 description 22
- 239000003921 oil Substances 0.000 description 21
- 235000019198 oils Nutrition 0.000 description 21
- 244000043261 Hevea brasiliensis Species 0.000 description 17
- 229920003052 natural elastomer Polymers 0.000 description 17
- 229920001194 natural rubber Polymers 0.000 description 17
- 229920002635 polyurethane Polymers 0.000 description 17
- 239000004814 polyurethane Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000000463 material Substances 0.000 description 14
- 230000003712 anti-aging effect Effects 0.000 description 13
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 11
- 230000001133 acceleration Effects 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 10
- 239000011593 sulfur Substances 0.000 description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 8
- 235000021355 Stearic acid Nutrition 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 7
- 239000008117 stearic acid Substances 0.000 description 7
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 6
- 238000012650 click reaction Methods 0.000 description 6
- 229920003051 synthetic elastomer Polymers 0.000 description 6
- 239000005061 synthetic rubber Substances 0.000 description 6
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 5
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 5
- 229960002447 thiram Drugs 0.000 description 5
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000010692 aromatic oil Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000003505 terpenes Chemical class 0.000 description 4
- 235000007586 terpenes Nutrition 0.000 description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 4
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 4
- UJPKMTDFFUTLGM-UHFFFAOYSA-N 1-aminoethanol Chemical compound CC(N)O UJPKMTDFFUTLGM-UHFFFAOYSA-N 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 3
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 3
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 description 3
- 239000012991 xanthate Substances 0.000 description 3
- RQHGZNBWBKINOY-PLNGDYQASA-N (z)-4-tert-butylperoxy-4-oxobut-2-enoic acid Chemical compound CC(C)(C)OOC(=O)\C=C/C(O)=O RQHGZNBWBKINOY-PLNGDYQASA-N 0.000 description 2
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SZAQZZKNQILGPU-UHFFFAOYSA-N 2-[1-(2-hydroxy-3,5-dimethylphenyl)-2-methylpropyl]-4,6-dimethylphenol Chemical compound C=1C(C)=CC(C)=C(O)C=1C(C(C)C)C1=CC(C)=CC(C)=C1O SZAQZZKNQILGPU-UHFFFAOYSA-N 0.000 description 2
- KKYSBGWCYXYOHA-UHFFFAOYSA-N 3-methylthiopropylamine Chemical compound CSCCCN KKYSBGWCYXYOHA-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 244000020518 Carthamus tinctorius Species 0.000 description 2
- 235000003255 Carthamus tinctorius Nutrition 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 201000011510 cancer Diseases 0.000 description 2
- 229920003211 cis-1,4-polyisoprene Polymers 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 239000011280 coal tar Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 2
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 description 2
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000013013 elastic material Substances 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 2
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- ZICNIEOYWVIEQJ-UHFFFAOYSA-N (2-methylbenzoyl) 2-methylbenzenecarboperoxoate Chemical compound CC1=CC=CC=C1C(=O)OOC(=O)C1=CC=CC=C1C ZICNIEOYWVIEQJ-UHFFFAOYSA-N 0.000 description 1
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- NOBYOEQUFMGXBP-UHFFFAOYSA-N (4-tert-butylcyclohexyl) (4-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)OOC(=O)OC1CCC(C(C)(C)C)CC1 NOBYOEQUFMGXBP-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- JAEZSIYNWDWMMN-UHFFFAOYSA-N 1,1,3-trimethylthiourea Chemical compound CNC(=S)N(C)C JAEZSIYNWDWMMN-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
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- JSCFNQDWXBNVBP-UHFFFAOYSA-N 1,2-diphenylguanidine;phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O.C=1C=CC=CC=1N=C(N)NC1=CC=CC=C1 JSCFNQDWXBNVBP-UHFFFAOYSA-N 0.000 description 1
- PAEWNKLGPBBWNM-UHFFFAOYSA-N 1,3,5-tris[2-(3-sulfanylbutoxy)ethyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(S)CCOCCN1C(=O)N(CCOCCC(C)S)C(=O)N(CCOCCC(C)S)C1=O PAEWNKLGPBBWNM-UHFFFAOYSA-N 0.000 description 1
- KWPNNZKRAQDVPZ-UHFFFAOYSA-N 1,3-bis(2-methylphenyl)thiourea Chemical compound CC1=CC=CC=C1NC(=S)NC1=CC=CC=C1C KWPNNZKRAQDVPZ-UHFFFAOYSA-N 0.000 description 1
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
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- SQZCAOHYQSOZCE-UHFFFAOYSA-N 1-(diaminomethylidene)-2-(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N=C(N)N=C(N)N SQZCAOHYQSOZCE-UHFFFAOYSA-N 0.000 description 1
- GPRYVSOUOYKCHJ-UHFFFAOYSA-N 1-[chloro(fluoro)methoxy]-1,1,2,3,3,3-hexafluoropropane Chemical compound FC(Cl)OC(F)(F)C(F)C(F)(F)F GPRYVSOUOYKCHJ-UHFFFAOYSA-N 0.000 description 1
- ZQXIMYREBUZLPM-UHFFFAOYSA-N 1-aminoethanethiol Chemical compound CC(N)S ZQXIMYREBUZLPM-UHFFFAOYSA-N 0.000 description 1
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 description 1
- ILVIYRLLZTXZQL-UHFFFAOYSA-N 1-dimethoxyphosphoryl-2,2-dimethylpropan-1-one Chemical compound COP(=O)(OC)C(=O)C(C)(C)C ILVIYRLLZTXZQL-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- ZRMMVODKVLXCBB-UHFFFAOYSA-N 1-n-cyclohexyl-4-n-phenylbenzene-1,4-diamine Chemical compound C1CCCCC1NC(C=C1)=CC=C1NC1=CC=CC=C1 ZRMMVODKVLXCBB-UHFFFAOYSA-N 0.000 description 1
- MINNIIWBFAPUKJ-UHFFFAOYSA-N 1-n-octyl-4-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NCCCCCCCC)=CC=C1NC1=CC=CC=C1 MINNIIWBFAPUKJ-UHFFFAOYSA-N 0.000 description 1
- ZKEUVTROUPQVTM-UHFFFAOYSA-N 1-pentylperoxypentane Chemical compound CCCCCOOCCCCC ZKEUVTROUPQVTM-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- RMOWPZIKLZMJEV-UHFFFAOYSA-N 2,2,4-trimethyl-n-phenyl-1h-quinolin-6-amine Chemical compound C1=C2C(C)=CC(C)(C)NC2=CC=C1NC1=CC=CC=C1 RMOWPZIKLZMJEV-UHFFFAOYSA-N 0.000 description 1
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- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 239000008165 rice bran oil Substances 0.000 description 1
- 238000010074 rubber mixing Methods 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 235000011803 sesame oil Nutrition 0.000 description 1
- 239000008159 sesame oil Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
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- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- KQYLUTYUZIVHND-UHFFFAOYSA-N tert-butyl 2,2-dimethyloctaneperoxoate Chemical compound CCCCCCC(C)(C)C(=O)OOC(C)(C)C KQYLUTYUZIVHND-UHFFFAOYSA-N 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- ROEHNQZQCCPZCH-UHFFFAOYSA-N tert-butyl 2-tert-butylperoxycarbonylbenzoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1C(=O)OC(C)(C)C ROEHNQZQCCPZCH-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- BWSZXUOMATYHHI-UHFFFAOYSA-N tert-butyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(C)(C)C BWSZXUOMATYHHI-UHFFFAOYSA-N 0.000 description 1
- 229920003212 trans-1,4-polyisoprene Polymers 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 description 1
- RKQOSDAEEGPRER-UHFFFAOYSA-L zinc diethyldithiocarbamate Chemical compound [Zn+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S RKQOSDAEEGPRER-UHFFFAOYSA-L 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- NEYNBSGIXOOZGZ-UHFFFAOYSA-L zinc;butoxymethanedithioate Chemical compound [Zn+2].CCCCOC([S-])=S.CCCCOC([S-])=S NEYNBSGIXOOZGZ-UHFFFAOYSA-L 0.000 description 1
- AUMBZPPBWALQRO-UHFFFAOYSA-L zinc;n,n-dibenzylcarbamodithioate Chemical compound [Zn+2].C=1C=CC=CC=1CN(C(=S)[S-])CC1=CC=CC=C1.C=1C=CC=CC=1CN(C(=S)[S-])CC1=CC=CC=C1 AUMBZPPBWALQRO-UHFFFAOYSA-L 0.000 description 1
- JGSUMMPGKPITGK-UHFFFAOYSA-L zinc;n,n-dipentylcarbamodithioate Chemical compound [Zn+2].CCCCCN(C([S-])=S)CCCCC.CCCCCN(C([S-])=S)CCCCC JGSUMMPGKPITGK-UHFFFAOYSA-L 0.000 description 1
- QUPAJUAGQJQKQE-UHFFFAOYSA-L zinc;n,n-dipropylcarbamodithioate Chemical compound [Zn+2].CCCN(C([S-])=S)CCC.CCCN(C([S-])=S)CCC QUPAJUAGQJQKQE-UHFFFAOYSA-L 0.000 description 1
- LAGTXXPOZSLGSF-UHFFFAOYSA-L zinc;n-butyl-n-phenylcarbamodithioate Chemical compound [Zn+2].CCCCN(C([S-])=S)C1=CC=CC=C1.CCCCN(C([S-])=S)C1=CC=CC=C1 LAGTXXPOZSLGSF-UHFFFAOYSA-L 0.000 description 1
- KMNUDJAXRXUZQS-UHFFFAOYSA-L zinc;n-ethyl-n-phenylcarbamodithioate Chemical compound [Zn+2].CCN(C([S-])=S)C1=CC=CC=C1.CCN(C([S-])=S)C1=CC=CC=C1 KMNUDJAXRXUZQS-UHFFFAOYSA-L 0.000 description 1
- XGTKIWKDACDPMK-UHFFFAOYSA-L zinc;n-hexadecyl-n-propan-2-ylcarbamodithioate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCN(C(C)C)C([S-])=S.CCCCCCCCCCCCCCCCN(C(C)C)C([S-])=S XGTKIWKDACDPMK-UHFFFAOYSA-L 0.000 description 1
- XIRMSEKPPCLFNS-UHFFFAOYSA-L zinc;n-octadecyl-n-propan-2-ylcarbamodithioate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCCN(C(C)C)C([S-])=S.CCCCCCCCCCCCCCCCCCN(C(C)C)C([S-])=S XIRMSEKPPCLFNS-UHFFFAOYSA-L 0.000 description 1
- YBKBEKGVHFHCRI-UHFFFAOYSA-L zinc;piperidine-1-carbodithioate Chemical compound [Zn+2].[S-]C(=S)N1CCCCC1.[S-]C(=S)N1CCCCC1 YBKBEKGVHFHCRI-UHFFFAOYSA-L 0.000 description 1
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6576—Compounds of group C08G18/69
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D30/00—Producing pneumatic or solid tyres or parts thereof
- B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
- B29D30/08—Building tyres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D30/00—Producing pneumatic or solid tyres or parts thereof
- B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
- B29D30/08—Building tyres
- B29D30/10—Building tyres on round cores, i.e. the shape of the core is approximately identical with the shape of the completed tyre
- B29D30/16—Applying the layers; Guiding or stretching the layers during application
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
- C08G18/696—Polymers of conjugated dienes containing heteroatoms other than oxygen and other than the heteroatoms of copolymerised vinyl monomers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J115/00—Adhesives based on rubber derivatives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2475/00—Presence of polyurethane
Definitions
- the present disclosure relates to a reactive solvent-free adhesive composition and a method of manufacturing a tire using the same, and more specifically, to a reactive solvent-free adhesive composition for chemical bonding of a non-polar vulcanized rubber and a polar polyurethane material and a method of manufacturing a tire using the same.
- Vulcanized rubber is generally rubber which realizes elasticity by introducing a network structure into a polymer system obtained from a diene monomer using sulfur.
- the vulcanized rubber has widely been used as material for various tires, rollers, shoe soles, automobile parts and others since the vulcanized rubber is excellent in elasticity, durability and economic efficiency.
- Raw materials of the vulcanized rubber are raw materials such as natural rubber, styrene-butadiene copolymer rubber, butadiene rubber, acrylonitrile-butadiene copolymer, etc. most of which have low polarity values or non-polar characteristics.
- materials complementing disadvantages of the vulcanized rubber are frequently high polarity materials including polyurethane.
- An objective of the present disclosure is to provide a reactive solvent-free adhesive composition enabling parts in which non-polar elastomers such as vulcanized rubber and polar elastomers such as polyurethane are bonded to consistently maintain adhesive force even under severe conditions.
- the other objective of the present disclosure is to provide a method of manufacturing a tire in which a tread for a vulcanized rubber tire and rubber of a polyurethane material are chemically bonded using the adhesive composition.
- a reactive solvent-free adhesive composition comprises: a polybutadiene polyol; a compound having a thiol group; and a radical initiator.
- the reactive solvent-free adhesive composition may comprise 90 to 95 parts by weight of the polybutadiene polyol, 5 to 10 parts by weight of the compound having a thiol group, and 0.1 to 5 parts by weight of the radical initiator.
- polybutadiene polyol may be any one selected from the group consisting of cis-1,4-polybutadiene polyol, trans-1,4-polybutadiene polyol, 1,2-polybutadiene polyol, and hydroxyl-terminated polybutadiene, or mixtures of two or more thereof.
- the compound having a thiol group may be an aliphatic thiol compound or an aromatic thiol compound.
- radical initiator may be any one selected from the group consisting of a photoinitiator, a peroxide initiator, and an azo compound, or mixtures of two or more thereof.
- a method of manufacturing a tire according to the other aspect of the present disclosure comprises: a step (S1) of applying an adhesive composition to the surface of a vulcanized rubber for tire tread; a step (S2) of forming a polyurethane prepolymer on the adhesive composition; and a step (S3) of heating a resulting product of the step (S2), wherein the adhesive composition is the aforementioned reactive solvent-free adhesive composition according to the present disclosure.
- An adhesive composition according to the present disclosure enables realization of high adhesive force through chemical bonding in an interface between a vulcanized rubber and polyurethane by comprising a polybutadiene polyol capable of being chemically bonded with a non-polar vulcanized rubber and a thiol compound capable of participating in the formation of a polar polyurethane material.
- an adhesive composition according to the present disclosure is environmentally friendly since the adhesive composition according to the present disclosure does not comprise an organic solvent differently from conventional adhesive compositions.
- a reactive solvent-free adhesive composition comprises: a polybutadiene polyol; a compound having a thiol group; and a radical initiator.
- the polybutadiene polyol can be chemically bonded to a non-polar vulcanized rubber.
- the polybutadiene polyol as an oligomer obtained by polymerizing butadiene, is well applied to an adherend surface and wets the vulcanized rubber well by having excellent affinity with respect to a vulcanized rubber. Further, the polybutadiene polyol enables a remaining double bond to be chemically bonded to a double bond of the vulcanized rubber even after the polybutadiene polyol has been formed into an oligomer.
- hydroxyl groups introduced into the polybutadiene polyol may have reactivity capable of being participated in the formation of a polar elastic material such as polyurethane to be adhered to the vulcanized rubber. Such multiple reactivities enable realization of high adhesive force due to chemical bonding between adherend surfaces.
- the polybutadiene polyol additionally includes a compound having a thiol group in the present disclosure since it is difficult to use the polybutadiene polyol alone due to high viscosity at room temperature although the polybutadiene polyol generally has a weight average molecular weight of 10,000 g/mol or less.
- the compound having a thiol group can participate in the formation of a polar elastic material such as polyurethane as well as reaction with the polybutadiene polyol.
- a compound having a thiol group can form a double bond and a covalent bond through a so-called thiol-ene click reaction, has reactivity capable of participating even in the formation of a polyurethane material, has low viscosity, and exhibits compatibility with the polybutadiene polyol.
- FIG. 1 illustrates that a polybutadiene polyol (hydroxyl terminated polybutadiene, HTPB) and a compound (HS-CH 2 CH 2 OH) having a thiol group are subjected to a thiol-ene click reaction by a radical initiator. Radical initiators are needed in order for such a thiol-ene click reaction to be occurred.
- FIG. 2 is a drawing illustrating a reaction of forming polyurethane by a chemical reaction between a thiol compound and a polyurethane prepolymer
- FIG. 3 is a drawing illustrating a reaction of forming polyurethane by a chemical reaction between a hydroxyl group-containing compound and the polyurethane prepolymer. Strong adhesive force can be realized since a chemical reaction occurs in an interface coupled to a polar polyurethane prepolymer through reactions such as those of FIG. 2 and FIG. 3 .
- the reactive solvent-free adhesive composition may comprise 90 to 95 parts by weight of the polybutadiene polyol, 5 to 10 parts by weight of the compound having a thiol group, and 0.1 to 5 parts by weight of the radical initiator.
- the reactive solvent-free adhesive composition may have a problem due to phase separation between the polybutadiene polyol and the compound having the thiol group when the reactive solvent-free adhesive composition comprises less than 90 parts by weight of the polybutadiene polyol and more than 10 parts by weight of the compound having the thiol group, while the reactive solvent-free adhesive composition may exhibit low adhesive strength when the reactive solvent-free adhesive composition comprises more than 95 parts by weight of the polybutadiene polyol and less than 5 parts by weight of the compound having the thiol group.
- a smooth reaction may not be generated in the reactive solvent-free adhesive composition due to shortfall of an initiator content when the reactive solvent-free adhesive composition comprises less than 0.1 part by weight of the radical initiator, while proper adhesive application may be impossible due to too fast reaction when the reactive solvent-free adhesive composition comprises more than 5 parts by weight of the radical initiator.
- the polybutadiene polyol for preparing a reactive solvent-free adhesive composition may include any one selected from the group consisting of cis-1,4-polybutadiene polyol, trans-1,4-polybutadiene polyol, 1,2-polybutadiene polyol, and hydroxyl-terminated polybutadiene, or mixtures of two or more thereof.
- the compound having the thiol group may be an aliphatic thiol compound or an aromatic thiol compound.
- nonlimiting examples of the thiol compound may include: aliphatic thiol compounds such as 1,3-propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,7-heptanedithiol, 1,8-octanedithiol, 2-mercaptoethanol, aminoethanethiol, 2-(butylamino)ethanethiol, 3-(methylthio)propylamine, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), pentaerythritol tetrakis(thioglycolate), tris[(3-mercaptol,
- the radical initiator may be any one selected from the group consisting of a photoinitiator activated by ultraviolet rays, a peroxide initiator using decomposition accomplished by heating, and an azo compound, or mixtures of two or more thereof.
- the photoinitiator may include benzoin ether (e.g., benzoin methyl ether or benzoin butyl ether), an acetophenone derivative (e.g., 2,2-dimethoxy-2-phenylacetophenone or 2,2-diethoxyacetophenone), 1-hydroxycyclohexyl phenyl ketone, an acylphosphine oxide derivative, and an acylphosphonate derivative (e.g., bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, isopropoxyphenyl-2,4,6-trimethylbenzoylphosphine oxide, or dimethyl pivaloylphosphonate).
- benzoin ether e.g., benzoin methyl ether or benzoin butyl ether
- an acetophenone derivative e.g., 2,2-dimethoxy-2-phenylacetophenone
- the peroxide initiator may include hydroperoxide (e.g., cumene, tert-butyl hydroperoxide or tert-amyl hydroperoxide), dialkyl peroxide (e.g., di-tert-butyl peroxide, dicumyl peroxide or cyclohexyl peroxide), peroxyester (e.g., tert-butyl perbenzoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl monoperoxymaleate, or di-tert-butyl peroxyphthalate), and diacyl peroxide (e.g., benzoyl peroxide or lauryl peroxide).
- hydroperoxide e.g., cumene, tert-butyl hydroperoxide or tert-amyl hydroperoxide
- the peroxide initiator may include peroxycarbonate (e.g., tert-butylperoxy 2-ethylhexyl carbonate, tert-butylperoxy isopropyl carbonate, or di(4-tert-butylcyclohexyl)peroxydicarbonate) and ketone peroxides (e.g., methyl ethyl ketone peroxide, 1,1-di(tert-butylperoxy)cyclohexane, 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, and cyclohexanone peroxide).
- peroxycarbonate e.g., tert-butylperoxy 2-ethylhexyl carbonate, tert-butylperoxy isopropyl carbonate, or di(4-tert-butylcyclohexyl)peroxydicarbonate
- the azo compound may include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 1,1'-azobis(1-cyclohexanecarbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis-(N,N'-dimethyleneisobutyramidine) dihydrochloride and 2,2'-azobis(2-amidinopropane) dihydrochloride, and organic or inorganic peroxides such as diacetyl peroxide, di-tert-butyl peroxide, diamyl peroxide, dioctanoyl peroxide, dodecanoyl peroxide, dilauroyl peroxide, benzoyl peroxide, bis(o-toluoyl) peroxide, succinyl peroxide
- Such a radical initiator may be generally used in an amount of 0.1 to 5 wt% based on the total amount of a monomer, more preferably in an amount of 0.1 to 3 wt% based on the total amount of the monomer.
- a method of manufacturing a tire according to the other aspect of the present disclosure comprises: a step (S1) of applying an adhesive composition to the surface of a vulcanized rubber for tire tread; a step (S2) of forming a polyurethane prepolymer on the adhesive composition; and a step (S3) of heating a resulting product of the step (S2), wherein the adhesive composition is the aforementioned reactive solvent-free adhesive composition according to the present disclosure.
- adhesive force between the two materials can be perfectly realized by performing chemical bonding between the vulcanized rubber for tire tread and the polyurethane prepolymer.
- the method of manufacturing the tire comprises performing a heat treatment process at 110 °C for 30 minutes such that a thiol-ene click reaction can be proceeded by an adhesive composition after the step (S1) and before the step (S2).
- step (S3) may be performed at 110 °C for 12 hours to cure polyurethane.
- a raw rubber of a vulcanized rubber for tire tread may be any one selected from the group consisting of a natural rubber, a synthetic rubber, and a combination thereof.
- the natural rubber may be a general natural rubber or a modified natural rubber.
- the general natural rubber may include any rubbers which have been known as a natural rubber without limiting place of origin or the like thereof.
- the natural rubber includes cis-1,4-polyisoprene as a main body, but may include trans-1,4-polyisoprene according to required characteristics. Therefore, the natural rubber may also include a natural rubber including trans-1,4-isoprene as a main body, e.g., balata or the like, i.e., a type of South American Sapotaceae rubber besides the natural rubber including cis-1,4-polyisoprene as a main body.
- the modified natural rubber means a natural rubber obtained by modifying or purifying the general natural rubber.
- the modified natural rubber may include an epoxidized natural rubber (ENR), a deproteinized natural rubber (DPNR), a hydrogenated natural runner, etc.
- the synthetic rubber may be any one selected from the group consisting of styrene butadiene rubber (SBR), modified styrene butadiene rubber, butadiene rubber (BR), modified butadiene rubber, acrylonitrile butadiene rubber, and combinations thereof.
- SBR styrene butadiene rubber
- BR butadiene rubber
- acrylonitrile butadiene rubber acrylonitrile butadiene rubber
- the raw rubber among these materials includes a mixture of styrene butadiene rubber (SBR) and butadiene rubber (BR).
- SBR styrene butadiene rubber
- BR butadiene rubber
- a reinforcing filler may include carbon black, silica, or a mixture thereof.
- a vulcanized rubber composition for the tire tread may further comprise optionally additional various additives including a vulcanizing agent, a vulcanization accelerator, a vulcanization acceleration aid, an antiaging agent, a softener, a retarder, an adhesive, etc.
- the various additives may include any additives which are generally used in the art to which the present disclosure pertains, and amounts of the additives are in accordance with a mixing ratio used in a general rubber composition for tire tread. Therefore, the amounts of the additives are not particularly limited.
- the vulcanizing agent may preferably include a sulfur-based vulcanizing agent.
- the sulfur-based vulcanizing agent may include an inorganic vulcanizing agent such as sulfur (S) powder, insoluble sulfur (S), precipitated sulfur (S), colloidal sulfur, etc.
- the sulfur-based vulcanizing agent may include a vulcanizing agent for producing element sulfur or sulfur, e.g., amine disulfide, polymer sulfur, etc.
- the vulcanizing agent is preferably included in an amount of 0.5 to 4.0 parts by weight with respect to 100 parts by weight of the raw rubber in that the vulcanizing agent makes the raw rubber less sensitive to heat and allows the raw rubber to be chemically stable as appropriate vulcanizing effects.
- the vulcanization accelerator means an accelerator which accelerates vulcanization rate or accelerates delayed action in an initial vulcanization step.
- the vulcanization accelerator may include any one selected from the group consisting of a sulfenamide-based vulcanization accelerator, a thiazole-based vulcanization accelerator, a thiuram-based vulcanization accelerator, a thiourea-based vulcanization accelerator, a guanidine-based vulcanization accelerator, a dithiocarbamic acid-based vulcanization accelerator, an aldehyde-amine based vulcanization accelerator, an aldehyde-ammonia based vulcanization accelerator, an imidazoline-based vulcanization accelerator, a xanthate-based vulcanization accelerator, and combinations thereof.
- the sulfenamide-based vulcanization accelerator may include any one sulfenamide-based compound selected from the group consisting of N-cyclohexyl-2-benzothiazolesulfenamide (CBS), N-tert-butyl-2-benzothiazolesulfenamide (TBBS), N,N-dicyclohexyl-2-benzothiazolesulfenamide, N-oxydiethylene-2-benzothiazolesulfenamide, N,N-diisopropyl-2-benzothiazolesulfenamide, and combinations thereof.
- CBS N-cyclohexyl-2-benzothiazolesulfenamide
- TBBS N-tert-butyl-2-benzothiazolesulfenamide
- N,N-dicyclohexyl-2-benzothiazolesulfenamide N-oxydiethylene-2-benzothiazolesulfenamide
- the thiazole-based vulcanization accelerator may include any one thiazole-based compound selected from the group consisting of 2-mercaptobenzothiazole (MBT), dibenzothiazole disulfide (MBTS), a sodium salt of 2-mercaptobenzothiazole, a zinc salt of 2-mercaptobenzothiazole, a copper salt of 2-mercaptobenzothiazole, a cyclohexylamine salt of 2-mercaptobenzothiazole, 2-(2,4-dinitrophenyl)mercaptobenzothiazole, 2-(2,6-diethyl-4-morpholinothio)benzothiazole, and combinations thereof.
- MTT 2-mercaptobenzothiazole
- MBTS dibenzothiazole disulfide
- a sodium salt of 2-mercaptobenzothiazole a zinc salt of 2-mercaptobenzothiazole
- a copper salt of 2-mercaptobenzothiazole a cyclohexy
- the thiuram-based vulcanization accelerator may include any one thiuram-based compound selected from the group consisting of tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide, tetramethylthiuram monosulfide, dipentamethylenethiuram disulfide, dipentamethylenethiuram monosulfide, dipentamethylenethiuram tetrasulfide, dipentamethylenethiuram hexasulfide, tetrabutylthiuram disulfide, pentamethylenethiuram tetrasulfide, and combinations thereof.
- TMTD tetramethylthiuram disulfide
- TMTD tetraethylthiuram disulfide
- tetramethylthiuram monosulfide dipentamethylenethiuram disulfide
- dipentamethylenethiuram disulfide dipentamethylenethiuram monosul
- the thiourea-based vulcanization accelerator may include any one thiourea-based compound selected from the group consisting of thiocarbamide, diethylthiourea, dibutylthiourea, trimethylthiourea, Di-o-tolylthiourea, and combinations thereof.
- the guanidine-based vulcanization accelerator may include any one guanidine-based compound selected from the group consisting of diphenylguanidine, Di-o-tolylguanidine, triphenylguanidine, o-Tolylbiguanide, diphenylguanidine phthalate, and combinations thereof.
- the dithiocarbamic acid-based vulcanization accelerator may include any one dithiocarbamic acid-based compound selected from the group consisting of zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, zinc diamyldithiocarbamate, zinc dipropyldithiocarbamate, a complex salt of zinc pentamethylenedithiocarbamate and piperidine, zinc hexadecylisopropyldithiocarbamate, zinc octadecylisopropyldithiocarbamate, zinc dibenzyldithiocarbamate, sodium diethyldithiocarbamate, piperidine pentamethylenedithiocarbamate, seleni
- the aldehyde-amine based or aldehyde-ammonia based vulcanization accelerator may include an aldehyde-amine based or aldehyde-ammonia based compound selected from the group consisting of an acetaldehyde-aniline reactant, a butylaldehyde-aniline condensate, hexamethylenetetramine, an acetaldehyde-ammonia reactant, and combinations thereof.
- the imidazoline-based vulcanization accelerator may include imidazoline-based compounds such as 2-mercaptoimidazoline, etc.
- the xanthate-based vulcanization accelerator may include xanthate-based compounds such as zinc dibutylxanthate, etc.
- the vulcanization accelerator may be included in an amount of 0.5 to 4.0 parts by weight with respect to 100 parts by weight of the raw rubber to maximize improvements in productivity and rubber physical properties through acceleration of vulcanization rate.
- the vulcanization acceleration aid as a compounding agent which is used in a combination with the vulcanization accelerator to complete its acceleration effect, may include any one selected from the group consisting of an inorganic vulcanization acceleration aid, an organic vulcanization acceleration aid, and a combination thereof.
- the inorganic vulcanization acceleration aid may include any one selected from the group consisting of zinc oxide (ZnO), zinc carbonate, magnesium oxide (MgO), lead oxide, potassium hydroxide, and combinations thereof.
- the organic vulcanization acceleration aid may include any one selected from the group consisting of stearic acid, zinc stearate, palmitic acid, linoleic acid, oleic acid, lauric acid, dibutyl ammonium oleate, derivatives thereof, and combinations thereof.
- the zinc oxide and the stearic acid may be used together as the vulcanization acceleration aid.
- a crosslinking reaction of rubber is facilitated by dissolving the lead oxide in the stearic acid, thereby producing sulfur favorable to a vulcanization reaction by forming an effective complex with the vulcanization accelerator.
- the zinc oxide and the stearic acid may respectively be used in amounts of 1 to 5 parts by weight and 0.5 to 3 parts by weight with respect to 100 parts by weight of the raw rubber in order to perform an appropriate role as the vulcanization acceleration aid when the zinc oxide and the stearic acid are used together.
- Productivity may be deteriorated since vulcanization rate is slow when the zinc oxide and the stearic acid are used in amounts less than the ranges, while physical properties may be lowered since a scorch phenomenon occurs when the zinc oxide and the stearic acid are used in amounts more than the ranges.
- the antiaging agent is an additive which is used to stop a chain reaction in which a tire is automatically oxidized by oxygen.
- the antiaging agent may include any one appropriately selected from the group consisting of an amine-based antiaging agent, a phenolic antiaging agent, a quinoline-based antiaging agent, an imidazole-based antiaging agent, a carbamate metal salt, wax, and combinations thereof.
- the amine-based antiaging agent may include any one selected from the group consisting of N-phenyl-N'-(1,3-dimethyl)-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-diaryl-p-phenylenediamine, N-phenyl-N'-cyclohexyl-p-phenylenediamine, N-phenyl-N'-octyl-p-phenylenediamine, and combinations thereof.
- the phenolic antiaging agent may include any one selected from the group consisting of 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 2,2'-isobutylidene-bis(4,6-dimethylphenol), 2,6-di-t-butyl-p-cresol, and combinations thereof.
- the quinoline-based antiaging agent may include 2,2,4-trimethyl-1,2-dihydroquinoline and derivatives thereof, specifically any one selected from the group consisting of 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, 6-anilino-2,2,4-trimethyl-1,2-dihydroquinoline, 6-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline, and combinations thereof.
- the wax preferably includes waxy hydrocarbons.
- the antiaging agent may be included in an amount of 1 to 10 parts by weight with respect to 100 parts by weight of the raw rubber considering conditions that the antiaging agent should have a high solubility for rubber besides an antiaging effect, should have a low volatility, should be inactive to rubber, and should not hinder vulcanization.
- the softener which is added to the rubber composition to facilitate processing or lower hardness of vulcanized rubber by giving plasticity to rubber means other oil materials used during rubber mixing or rubber manufacturing.
- the softener means oils included in process oil or other rubber compositions.
- the softener may include any one selected from the group consisting of a petroleum-based oil, a vegetable oil, and a combination thereof, the present disclosure is not limited thereto.
- the petroleum-based oil may include any one selected from the group consisting of a paraffin-based oil, a naphthene-based oil, an aromatic oil, and combinations thereof.
- Typical examples of the paraffin-based oil may include P-1, P-2, P-3, P-4, P-5, P-6, etc. of Michang Oil Industry Co., Ltd.
- typical examples of the naphthene-based oil may include N-1, N-2, N-3, etc. of Michang Oil Industry Co., Ltd.
- typical examples of the aromatic oil may include A-2, A-3, etc. of Michang Oil Industry Co., Ltd.
- the aromatic oil may preferably include a treated distillate aromatic extract (TDAE) oil, a mild extraction solvate (MES) oil, a residual aromatic extract (RAE) oil, or a heavy naphthenic oil.
- TDAE treated distillate aromatic extract
- MES mild extraction solvate
- RAE residual aromatic extract
- the oil used as the softener may preferably be TDAE oil in which components of PAHs are included in a total amount of 3 wt% or less with respect to the total oil weight, which has a kinematic viscosity of 95 or more (210 °F SUS), and which comprises 15 to 25 wt% of an aromatic component, 27 to 37 wt% of a naphthenic component, and 38 to 58 wt% of a paraffinic component in the softener.
- TDAE oil in which components of PAHs are included in a total amount of 3 wt% or less with respect to the total oil weight, which has a kinematic viscosity of 95 or more (210 °F SUS), and which comprises 15 to 25 wt% of an aromatic component, 27 to 37 wt% of a naphthenic component, and 38 to 58 wt% of a paraffinic component in the softener.
- the TDAE oil has characteristics advantageous even to environmental factors such as a cancer-causing possibility of PAHs while enabling a tire tread including the TDAE oil to maintain excellent low temperature characteristics and fuel efficiency performance.
- the vegetable oil may include any one selected from the group consisting of castor oil, cottonseed oil, linseed oil, canola oil, soybean oil, palm oil, coconut oil, peanut oil, pine oil, pine tar, tall oil, corn oil, rice bran oil, safflower oil, sesame oil, olive oil, sunflower oil, palm kernel oil, camellia oil, jojoba oil, Macadamia Nut Oil, Carthamus Tinctorius (Safflower) Seed Oil, Chinese wood oil, and combinations thereof.
- the softener is preferably included in an amount of 0 to 20 parts by weight with respect to 100 parts by weight of the raw rubber in that the softener improves processability of the raw rubber.
- the retarder may include any one selected from the group consisting of phthalate anhydride, salicylic acid, sodium acetate, N-cyclohexyl thiophthalimide, and combinations thereof.
- the retarder may be included in an amount of 0.1 to 0.5 part by weight with respect to 100 parts by weight of the raw rubber.
- the adhesive contributes to improvement in physical properties of the rubber composition by further improving tack performance between rubbers and improving mixability, dispersibility and processability of other additives including a filler.
- the adhesive may include a natural resin-based adhesive such as a rosin-based resin or a terpene-based resin, and a synthetic resin-based adhesive such as petroleum resin, coal tar, alkyl phenolic resin, etc.
- a natural resin-based adhesive such as a rosin-based resin or a terpene-based resin
- synthetic resin-based adhesive such as petroleum resin, coal tar, alkyl phenolic resin, etc.
- the rosin-based resin may be any one selected from the group consisting of a rosin resin, a rosin ester resin, a hydrogen-added rosin ester resin, derivatives thereof, and combinations thereof.
- the terpene-based resin may be any one selected from the group consisting of a terpene resin, a terpene phenol resin, and a combination thereof.
- the petroleum resin may be any one selected from the group consisting of an aliphatic resin, an acid-modified aliphatic resin, an alicyclic resin, a hydrogen-added alicyclic resin, an aromatic (C 9 ) resin, a hydrogen-added aromatic resin, a C 5 -C 9 copolymer resin, a styrene resin, a styrene copolymer resin, and combinations thereof.
- the coal tar may be coumarone-indene resin.
- the alkyl phenolic resin may be p-tert-alkylphenol formaldehyde resin or resorcinol formaldehyde resin, and the p-tert-alkylphenol formaldehyde resin may be any one selected from the group consisting of p-tert-butylphenol formaldehyde resin, p-tert-octyl phenol formaldehyde resin, and a combination thereof.
- the adhesive may be included in an amount of 2 to 4 parts by weight with respect to 100 parts by weight of the raw rubber. Adhesion performance of the rubber may become disadvantageous when the adhesive is included in an amount of less than 2 parts by weight with respect to 100 parts by weight of the raw rubber, while physical properties of the rubber may be deteriorated when the adhesive is included in an amount of more than 4 parts by weight with respect to 100 parts by weight of the raw rubber.
- the tire according to the present disclosure may be a tire for a passenger vehicle, a tire for a racing car, an aircraft tire, a tire for an agricultural machine, a tire for off-the-road driving, a truck tire, a bus tire, or the like. Further, the tire may be a radial tire or a bias tire.
- Adhesive compositions were prepared by the same compositions as represented in the following Table 1. The following adhesive compositions do not comprise an organic solvent.
- Table 1 Composition Example 1 Example 2 Example 3 Example 4 Polybutadiene polyol (Weight average molecular weight: 2,800 g/mol) 95 92.5 95 90 Compound having a thiol group 2-mercaptoethanol 5 7.5 - - 2,2-(ethylenedioxy)diethanethiol - - 5 10 Tert-butyl perbenzoate 2 2 2 2 2 2 2 2 2 2 2 2 2
- Adhesive force values typical vulcanized synthetic rubbers used as materials for tire tread and polyurethane elastomers having a Shore A harness level of 95 were measured to measure adhesive force values according to adhesive compositions prepared in the Examples.
- the adhesive compositions applied to the vulcanized synthetic rubbers were heat-treated at 110 °C for 30 minutes such that the vulcanized rubbers were sufficiently dipped in the adhesive compositions, and a thiol-ene click reaction was carried out.
- Example 1 Example 2
- Example 3 Example 4 T-peel adhesive force (kgf/cm) between polyurethane and vulcanized rubbers 11.72 12.06 11.87 13.21
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Abstract
Description
- The present disclosure relates to a reactive solvent-free adhesive composition and a method of manufacturing a tire using the same, and more specifically, to a reactive solvent-free adhesive composition for chemical bonding of a non-polar vulcanized rubber and a polar polyurethane material and a method of manufacturing a tire using the same.
- Vulcanized rubber is generally rubber which realizes elasticity by introducing a network structure into a polymer system obtained from a diene monomer using sulfur. The vulcanized rubber has widely been used as material for various tires, rollers, shoe soles, automobile parts and others since the vulcanized rubber is excellent in elasticity, durability and economic efficiency.
- Since it is limited to satisfy required performance with a single material of the vulcanized rubber when using such a vulcanized rubber in manufacturing of various products such as automobile parts, tires, shoes, etc., it is necessary to composite the vulcanized rubber together with other material parts, and bonding using adhesive is required in this case.
- Raw materials of the vulcanized rubber are raw materials such as natural rubber, styrene-butadiene copolymer rubber, butadiene rubber, acrylonitrile-butadiene copolymer, etc. most of which have low polarity values or non-polar characteristics.
- Meanwhile, materials complementing disadvantages of the vulcanized rubber are frequently high polarity materials including polyurethane. There is a problem that it is difficult to realize required performance when using a general adhesive using surface physical bonding to bond such materials with the vulcanized rubber.
- An objective of the present disclosure is to provide a reactive solvent-free adhesive composition enabling parts in which non-polar elastomers such as vulcanized rubber and polar elastomers such as polyurethane are bonded to consistently maintain adhesive force even under severe conditions.
- The other objective of the present disclosure is to provide a method of manufacturing a tire in which a tread for a vulcanized rubber tire and rubber of a polyurethane material are chemically bonded using the adhesive composition.
- In order to accomplish the objectives, a reactive solvent-free adhesive composition according to an aspect of the present disclosure comprises: a polybutadiene polyol; a compound having a thiol group; and a radical initiator.
- Herein, the reactive solvent-free adhesive composition may comprise 90 to 95 parts by weight of the polybutadiene polyol, 5 to 10 parts by weight of the compound having a thiol group, and 0.1 to 5 parts by weight of the radical initiator.
- Further, the polybutadiene polyol may be any one selected from the group consisting of cis-1,4-polybutadiene polyol, trans-1,4-polybutadiene polyol, 1,2-polybutadiene polyol, and hydroxyl-terminated polybutadiene, or mixtures of two or more thereof.
- In addition, the compound having a thiol group may be an aliphatic thiol compound or an aromatic thiol compound.
- Further, the radical initiator may be any one selected from the group consisting of a photoinitiator, a peroxide initiator, and an azo compound, or mixtures of two or more thereof.
- On the other hand, a method of manufacturing a tire according to the other aspect of the present disclosure comprises: a step (S1) of applying an adhesive composition to the surface of a vulcanized rubber for tire tread; a step (S2) of forming a polyurethane prepolymer on the adhesive composition; and a step (S3) of heating a resulting product of the step (S2), wherein the adhesive composition is the aforementioned reactive solvent-free adhesive composition according to the present disclosure.
- An adhesive composition according to the present disclosure enables realization of high adhesive force through chemical bonding in an interface between a vulcanized rubber and polyurethane by comprising a polybutadiene polyol capable of being chemically bonded with a non-polar vulcanized rubber and a thiol compound capable of participating in the formation of a polar polyurethane material.
- Further, an adhesive composition according to the present disclosure is environmentally friendly since the adhesive composition according to the present disclosure does not comprise an organic solvent differently from conventional adhesive compositions.
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FIG. 1 is a drawing illustrating that a polybutadiene polyol (hydroxyl terminated polybutadiene, HTPB) and a compound (HS-CH2CH2OH) having a thiol group according to an embodiment of the present disclosure are subjected to a thiol-ene click reaction by a radical initiator. -
FIG. 2 is a drawing illustrating a reaction of forming polyurethane by a chemical reaction between a thiol group of a thiol compound and a polyurethane prepolymer according to an embodiment of the present disclosure. -
FIG. 3 is a drawing illustrating a reaction of forming polyurethane by a chemical reaction between a hydroxyl group-containing compound and the polyurethane prepolymer according to an embodiment of the present disclosure. - Hereinafter, the present disclosure will be described in more detail.
- A reactive solvent-free adhesive composition according to an aspect of the present disclosure comprises: a polybutadiene polyol; a compound having a thiol group; and a radical initiator.
- The polybutadiene polyol can be chemically bonded to a non-polar vulcanized rubber. First, the polybutadiene polyol, as an oligomer obtained by polymerizing butadiene, is well applied to an adherend surface and wets the vulcanized rubber well by having excellent affinity with respect to a vulcanized rubber. Further, the polybutadiene polyol enables a remaining double bond to be chemically bonded to a double bond of the vulcanized rubber even after the polybutadiene polyol has been formed into an oligomer. Further, hydroxyl groups introduced into the polybutadiene polyol may have reactivity capable of being participated in the formation of a polar elastic material such as polyurethane to be adhered to the vulcanized rubber. Such multiple reactivities enable realization of high adhesive force due to chemical bonding between adherend surfaces.
- Meanwhile, the polybutadiene polyol additionally includes a compound having a thiol group in the present disclosure since it is difficult to use the polybutadiene polyol alone due to high viscosity at room temperature although the polybutadiene polyol generally has a weight average molecular weight of 10,000 g/mol or less.
- The compound having a thiol group can participate in the formation of a polar elastic material such as polyurethane as well as reaction with the polybutadiene polyol. Such a compound having a thiol group can form a double bond and a covalent bond through a so-called thiol-ene click reaction, has reactivity capable of participating even in the formation of a polyurethane material, has low viscosity, and exhibits compatibility with the polybutadiene polyol.
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FIG. 1 illustrates that a polybutadiene polyol (hydroxyl terminated polybutadiene, HTPB) and a compound (HS-CH2CH2OH) having a thiol group are subjected to a thiol-ene click reaction by a radical initiator. Radical initiators are needed in order for such a thiol-ene click reaction to be occurred. -
FIG. 2 is a drawing illustrating a reaction of forming polyurethane by a chemical reaction between a thiol compound and a polyurethane prepolymer, andFIG. 3 is a drawing illustrating a reaction of forming polyurethane by a chemical reaction between a hydroxyl group-containing compound and the polyurethane prepolymer. Strong adhesive force can be realized since a chemical reaction occurs in an interface coupled to a polar polyurethane prepolymer through reactions such as those ofFIG. 2 and FIG. 3 . - At this time, the reactive solvent-free adhesive composition may comprise 90 to 95 parts by weight of the polybutadiene polyol, 5 to 10 parts by weight of the compound having a thiol group, and 0.1 to 5 parts by weight of the radical initiator.
- The reactive solvent-free adhesive composition may have a problem due to phase separation between the polybutadiene polyol and the compound having the thiol group when the reactive solvent-free adhesive composition comprises less than 90 parts by weight of the polybutadiene polyol and more than 10 parts by weight of the compound having the thiol group, while the reactive solvent-free adhesive composition may exhibit low adhesive strength when the reactive solvent-free adhesive composition comprises more than 95 parts by weight of the polybutadiene polyol and less than 5 parts by weight of the compound having the thiol group.
- Further, a smooth reaction may not be generated in the reactive solvent-free adhesive composition due to shortfall of an initiator content when the reactive solvent-free adhesive composition comprises less than 0.1 part by weight of the radical initiator, while proper adhesive application may be impossible due to too fast reaction when the reactive solvent-free adhesive composition comprises more than 5 parts by weight of the radical initiator.
- On the other hand, the polybutadiene polyol for preparing a reactive solvent-free adhesive composition according to the present disclosure may include any one selected from the group consisting of cis-1,4-polybutadiene polyol, trans-1,4-polybutadiene polyol, 1,2-polybutadiene polyol, and hydroxyl-terminated polybutadiene, or mixtures of two or more thereof.
- In addition, the compound having the thiol group may be an aliphatic thiol compound or an aromatic thiol compound.
- More specifically, nonlimiting examples of the thiol compound may include: aliphatic thiol compounds such as 1,3-propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,7-heptanedithiol, 1,8-octanedithiol, 2-mercaptoethanol, aminoethanethiol, 2-(butylamino)ethanethiol, 3-(methylthio)propylamine, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), pentaerythritol tetrakis(thioglycolate), tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trion, pentaerythritol tetrakis(3-mercaptobutylate), 2,2'-(ethylenedioxy)diethanethiol, etc.; and aromatic thiol compounds, etc. Preferably, the nonlimiting examples of the thiol compound may be low molecular weight thiol compounds having a weight average molecular weight of about 500 g/mol or less.
- Further, the radical initiator may be any one selected from the group consisting of a photoinitiator activated by ultraviolet rays, a peroxide initiator using decomposition accomplished by heating, and an azo compound, or mixtures of two or more thereof.
- The photoinitiator may include benzoin ether (e.g., benzoin methyl ether or benzoin butyl ether), an acetophenone derivative (e.g., 2,2-dimethoxy-2-phenylacetophenone or 2,2-diethoxyacetophenone), 1-hydroxycyclohexyl phenyl ketone, an acylphosphine oxide derivative, and an acylphosphonate derivative (e.g., bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, isopropoxyphenyl-2,4,6-trimethylbenzoylphosphine oxide, or dimethyl pivaloylphosphonate).
- Further, the peroxide initiator may include hydroperoxide (e.g., cumene, tert-butyl hydroperoxide or tert-amyl hydroperoxide), dialkyl peroxide (e.g., di-tert-butyl peroxide, dicumyl peroxide or cyclohexyl peroxide), peroxyester (e.g., tert-butyl perbenzoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl monoperoxymaleate, or di-tert-butyl peroxyphthalate), and diacyl peroxide (e.g., benzoyl peroxide or lauryl peroxide).
- Further, the peroxide initiator may include peroxycarbonate (e.g., tert-butylperoxy 2-ethylhexyl carbonate, tert-butylperoxy isopropyl carbonate, or di(4-tert-butylcyclohexyl)peroxydicarbonate) and ketone peroxides (e.g., methyl ethyl ketone peroxide, 1,1-di(tert-butylperoxy)cyclohexane, 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, and cyclohexanone peroxide).
- Further, for example, the azo compound may include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 1,1'-azobis(1-cyclohexanecarbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis-(N,N'-dimethyleneisobutyramidine) dihydrochloride and 2,2'-azobis(2-amidinopropane) dihydrochloride, and organic or inorganic peroxides such as diacetyl peroxide, di-tert-butyl peroxide, diamyl peroxide, dioctanoyl peroxide, dodecanoyl peroxide, dilauroyl peroxide, benzoyl peroxide, bis(o-toluoyl) peroxide, succinyl peroxide, tert-butyl peracetate, tert-butyl permaleate, tert-butyl perisobutyrate, tert-butyl perpivalate, tert-butyl peroctoate, tert-butyl perneodecanoate, tert-butyl perbenzoate, tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxy-2-ethylhexanoate, and diisopropyl peroxydicarbamate.
- Such a radical initiator may be generally used in an amount of 0.1 to 5 wt% based on the total amount of a monomer, more preferably in an amount of 0.1 to 3 wt% based on the total amount of the monomer.
- On the other hand, a method of manufacturing a tire according to the other aspect of the present disclosure comprises: a step (S1) of applying an adhesive composition to the surface of a vulcanized rubber for tire tread; a step (S2) of forming a polyurethane prepolymer on the adhesive composition; and a step (S3) of heating a resulting product of the step (S2), wherein the adhesive composition is the aforementioned reactive solvent-free adhesive composition according to the present disclosure.
- According to the method, adhesive force between the two materials can be perfectly realized by performing chemical bonding between the vulcanized rubber for tire tread and the polyurethane prepolymer.
- At this time, the method of manufacturing the tire comprises performing a heat treatment process at 110 °C for 30 minutes such that a thiol-ene click reaction can be proceeded by an adhesive composition after the step (S1) and before the step (S2).
- Further, the step (S3) may be performed at 110 °C for 12 hours to cure polyurethane.
- Meanwhile, a raw rubber of a vulcanized rubber for tire tread according to the present disclosure may be any one selected from the group consisting of a natural rubber, a synthetic rubber, and a combination thereof.
- The natural rubber may be a general natural rubber or a modified natural rubber.
- The general natural rubber may include any rubbers which have been known as a natural rubber without limiting place of origin or the like thereof. The natural rubber includes cis-1,4-polyisoprene as a main body, but may include trans-1,4-polyisoprene according to required characteristics. Therefore, the natural rubber may also include a natural rubber including trans-1,4-isoprene as a main body, e.g., balata or the like, i.e., a type of South American Sapotaceae rubber besides the natural rubber including cis-1,4-polyisoprene as a main body.
- The modified natural rubber means a natural rubber obtained by modifying or purifying the general natural rubber. For example, the modified natural rubber may include an epoxidized natural rubber (ENR), a deproteinized natural rubber (DPNR), a hydrogenated natural runner, etc.
- Further, the synthetic rubber may be any one selected from the group consisting of styrene butadiene rubber (SBR), modified styrene butadiene rubber, butadiene rubber (BR), modified butadiene rubber, acrylonitrile butadiene rubber, and combinations thereof.
- It may be desirable in effect aspects of improving abrasion resistant performance and fuel efficiency performance of a tire according to use of raw rubber that the raw rubber among these materials includes a mixture of styrene butadiene rubber (SBR) and butadiene rubber (BR).
- Further, a reinforcing filler may include carbon black, silica, or a mixture thereof.
- On the other hand, a vulcanized rubber composition for the tire tread may further comprise optionally additional various additives including a vulcanizing agent, a vulcanization accelerator, a vulcanization acceleration aid, an antiaging agent, a softener, a retarder, an adhesive, etc. The various additives may include any additives which are generally used in the art to which the present disclosure pertains, and amounts of the additives are in accordance with a mixing ratio used in a general rubber composition for tire tread. Therefore, the amounts of the additives are not particularly limited.
- The vulcanizing agent may preferably include a sulfur-based vulcanizing agent. The sulfur-based vulcanizing agent may include an inorganic vulcanizing agent such as sulfur (S) powder, insoluble sulfur (S), precipitated sulfur (S), colloidal sulfur, etc. Specifically, the sulfur-based vulcanizing agent may include a vulcanizing agent for producing element sulfur or sulfur, e.g., amine disulfide, polymer sulfur, etc.
- The vulcanizing agent is preferably included in an amount of 0.5 to 4.0 parts by weight with respect to 100 parts by weight of the raw rubber in that the vulcanizing agent makes the raw rubber less sensitive to heat and allows the raw rubber to be chemically stable as appropriate vulcanizing effects.
- The vulcanization accelerator means an accelerator which accelerates vulcanization rate or accelerates delayed action in an initial vulcanization step.
- The vulcanization accelerator may include any one selected from the group consisting of a sulfenamide-based vulcanization accelerator, a thiazole-based vulcanization accelerator, a thiuram-based vulcanization accelerator, a thiourea-based vulcanization accelerator, a guanidine-based vulcanization accelerator, a dithiocarbamic acid-based vulcanization accelerator, an aldehyde-amine based vulcanization accelerator, an aldehyde-ammonia based vulcanization accelerator, an imidazoline-based vulcanization accelerator, a xanthate-based vulcanization accelerator, and combinations thereof.
- For example, the sulfenamide-based vulcanization accelerator may include any one sulfenamide-based compound selected from the group consisting of N-cyclohexyl-2-benzothiazolesulfenamide (CBS), N-tert-butyl-2-benzothiazolesulfenamide (TBBS), N,N-dicyclohexyl-2-benzothiazolesulfenamide, N-oxydiethylene-2-benzothiazolesulfenamide, N,N-diisopropyl-2-benzothiazolesulfenamide, and combinations thereof.
- For example, the thiazole-based vulcanization accelerator may include any one thiazole-based compound selected from the group consisting of 2-mercaptobenzothiazole (MBT), dibenzothiazole disulfide (MBTS), a sodium salt of 2-mercaptobenzothiazole, a zinc salt of 2-mercaptobenzothiazole, a copper salt of 2-mercaptobenzothiazole, a cyclohexylamine salt of 2-mercaptobenzothiazole, 2-(2,4-dinitrophenyl)mercaptobenzothiazole, 2-(2,6-diethyl-4-morpholinothio)benzothiazole, and combinations thereof.
- For example, the thiuram-based vulcanization accelerator may include any one thiuram-based compound selected from the group consisting of tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide, tetramethylthiuram monosulfide, dipentamethylenethiuram disulfide, dipentamethylenethiuram monosulfide, dipentamethylenethiuram tetrasulfide, dipentamethylenethiuram hexasulfide, tetrabutylthiuram disulfide, pentamethylenethiuram tetrasulfide, and combinations thereof.
- For example, the thiourea-based vulcanization accelerator may include any one thiourea-based compound selected from the group consisting of thiocarbamide, diethylthiourea, dibutylthiourea, trimethylthiourea, Di-o-tolylthiourea, and combinations thereof.
- For example, the guanidine-based vulcanization accelerator may include any one guanidine-based compound selected from the group consisting of diphenylguanidine, Di-o-tolylguanidine, triphenylguanidine, o-Tolylbiguanide, diphenylguanidine phthalate, and combinations thereof.
- For example, the dithiocarbamic acid-based vulcanization accelerator may include any one dithiocarbamic acid-based compound selected from the group consisting of zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, zinc diamyldithiocarbamate, zinc dipropyldithiocarbamate, a complex salt of zinc pentamethylenedithiocarbamate and piperidine, zinc hexadecylisopropyldithiocarbamate, zinc octadecylisopropyldithiocarbamate, zinc dibenzyldithiocarbamate, sodium diethyldithiocarbamate, piperidine pentamethylenedithiocarbamate, selenium dimethyldithiocarbamate, tellurium diethyldithiocarbamate, cadmium diamyldithiocarbamate, and combinations thereof.
- For example, the aldehyde-amine based or aldehyde-ammonia based vulcanization accelerator may include an aldehyde-amine based or aldehyde-ammonia based compound selected from the group consisting of an acetaldehyde-aniline reactant, a butylaldehyde-aniline condensate, hexamethylenetetramine, an acetaldehyde-ammonia reactant, and combinations thereof.
- For example, the imidazoline-based vulcanization accelerator may include imidazoline-based compounds such as 2-mercaptoimidazoline, etc., and the xanthate-based vulcanization accelerator may include xanthate-based compounds such as zinc dibutylxanthate, etc.
- The vulcanization accelerator may be included in an amount of 0.5 to 4.0 parts by weight with respect to 100 parts by weight of the raw rubber to maximize improvements in productivity and rubber physical properties through acceleration of vulcanization rate.
- Meanwhile, the vulcanization acceleration aid, as a compounding agent which is used in a combination with the vulcanization accelerator to complete its acceleration effect, may include any one selected from the group consisting of an inorganic vulcanization acceleration aid, an organic vulcanization acceleration aid, and a combination thereof.
- The inorganic vulcanization acceleration aid may include any one selected from the group consisting of zinc oxide (ZnO), zinc carbonate, magnesium oxide (MgO), lead oxide, potassium hydroxide, and combinations thereof. The organic vulcanization acceleration aid may include any one selected from the group consisting of stearic acid, zinc stearate, palmitic acid, linoleic acid, oleic acid, lauric acid, dibutyl ammonium oleate, derivatives thereof, and combinations thereof.
- Particularly, the zinc oxide and the stearic acid may be used together as the vulcanization acceleration aid. In this case, a crosslinking reaction of rubber is facilitated by dissolving the lead oxide in the stearic acid, thereby producing sulfur favorable to a vulcanization reaction by forming an effective complex with the vulcanization accelerator.
- The zinc oxide and the stearic acid may respectively be used in amounts of 1 to 5 parts by weight and 0.5 to 3 parts by weight with respect to 100 parts by weight of the raw rubber in order to perform an appropriate role as the vulcanization acceleration aid when the zinc oxide and the stearic acid are used together. Productivity may be deteriorated since vulcanization rate is slow when the zinc oxide and the stearic acid are used in amounts less than the ranges, while physical properties may be lowered since a scorch phenomenon occurs when the zinc oxide and the stearic acid are used in amounts more than the ranges.
- Meanwhile, the antiaging agent is an additive which is used to stop a chain reaction in which a tire is automatically oxidized by oxygen. The antiaging agent may include any one appropriately selected from the group consisting of an amine-based antiaging agent, a phenolic antiaging agent, a quinoline-based antiaging agent, an imidazole-based antiaging agent, a carbamate metal salt, wax, and combinations thereof.
- The amine-based antiaging agent may include any one selected from the group consisting of N-phenyl-N'-(1,3-dimethyl)-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-diaryl-p-phenylenediamine, N-phenyl-N'-cyclohexyl-p-phenylenediamine, N-phenyl-N'-octyl-p-phenylenediamine, and combinations thereof. The phenolic antiaging agent may include any one selected from the group consisting of 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 2,2'-isobutylidene-bis(4,6-dimethylphenol), 2,6-di-t-butyl-p-cresol, and combinations thereof. The quinoline-based antiaging agent may include 2,2,4-trimethyl-1,2-dihydroquinoline and derivatives thereof, specifically any one selected from the group consisting of 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, 6-anilino-2,2,4-trimethyl-1,2-dihydroquinoline, 6-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline, and combinations thereof. The wax preferably includes waxy hydrocarbons.
- Further, the antiaging agent may be included in an amount of 1 to 10 parts by weight with respect to 100 parts by weight of the raw rubber considering conditions that the antiaging agent should have a high solubility for rubber besides an antiaging effect, should have a low volatility, should be inactive to rubber, and should not hinder vulcanization.
- On the other hand, the softener which is added to the rubber composition to facilitate processing or lower hardness of vulcanized rubber by giving plasticity to rubber means other oil materials used during rubber mixing or rubber manufacturing. The softener means oils included in process oil or other rubber compositions. Although the softener may include any one selected from the group consisting of a petroleum-based oil, a vegetable oil, and a combination thereof, the present disclosure is not limited thereto.
- The petroleum-based oil may include any one selected from the group consisting of a paraffin-based oil, a naphthene-based oil, an aromatic oil, and combinations thereof.
- Typical examples of the paraffin-based oil may include P-1, P-2, P-3, P-4, P-5, P-6, etc. of Michang Oil Industry Co., Ltd., typical examples of the naphthene-based oil may include N-1, N-2, N-3, etc. of Michang Oil Industry Co., Ltd., and typical examples of the aromatic oil may include A-2, A-3, etc. of Michang Oil Industry Co., Ltd.
- However, since a cancer-causing possibility has been known to be high when polycyclic aromatic hydrocarbons (hereinafter, referred to as 'PAHs') included in the aromatic oil have a content of 3 wt% or more along with a recent upsurge of environmental consciousness, the aromatic oil may preferably include a treated distillate aromatic extract (TDAE) oil, a mild extraction solvate (MES) oil, a residual aromatic extract (RAE) oil, or a heavy naphthenic oil.
- Particularly, the oil used as the softener may preferably be TDAE oil in which components of PAHs are included in a total amount of 3 wt% or less with respect to the total oil weight, which has a kinematic viscosity of 95 or more (210 °F SUS), and which comprises 15 to 25 wt% of an aromatic component, 27 to 37 wt% of a naphthenic component, and 38 to 58 wt% of a paraffinic component in the softener.
- The TDAE oil has characteristics advantageous even to environmental factors such as a cancer-causing possibility of PAHs while enabling a tire tread including the TDAE oil to maintain excellent low temperature characteristics and fuel efficiency performance.
- The vegetable oil may include any one selected from the group consisting of castor oil, cottonseed oil, linseed oil, canola oil, soybean oil, palm oil, coconut oil, peanut oil, pine oil, pine tar, tall oil, corn oil, rice bran oil, safflower oil, sesame oil, olive oil, sunflower oil, palm kernel oil, camellia oil, jojoba oil, Macadamia Nut Oil, Carthamus Tinctorius (Safflower) Seed Oil, Chinese wood oil, and combinations thereof.
- The softener is preferably included in an amount of 0 to 20 parts by weight with respect to 100 parts by weight of the raw rubber in that the softener improves processability of the raw rubber.
- Meanwhile, the retarder may include any one selected from the group consisting of phthalate anhydride, salicylic acid, sodium acetate, N-cyclohexyl thiophthalimide, and combinations thereof. The retarder may be included in an amount of 0.1 to 0.5 part by weight with respect to 100 parts by weight of the raw rubber.
- Further, the adhesive contributes to improvement in physical properties of the rubber composition by further improving tack performance between rubbers and improving mixability, dispersibility and processability of other additives including a filler.
- The adhesive may include a natural resin-based adhesive such as a rosin-based resin or a terpene-based resin, and a synthetic resin-based adhesive such as petroleum resin, coal tar, alkyl phenolic resin, etc.
- The rosin-based resin may be any one selected from the group consisting of a rosin resin, a rosin ester resin, a hydrogen-added rosin ester resin, derivatives thereof, and combinations thereof. The terpene-based resin may be any one selected from the group consisting of a terpene resin, a terpene phenol resin, and a combination thereof.
- The petroleum resin may be any one selected from the group consisting of an aliphatic resin, an acid-modified aliphatic resin, an alicyclic resin, a hydrogen-added alicyclic resin, an aromatic (C9) resin, a hydrogen-added aromatic resin, a C5-C9 copolymer resin, a styrene resin, a styrene copolymer resin, and combinations thereof.
- The coal tar may be coumarone-indene resin.
- The alkyl phenolic resin may be p-tert-alkylphenol formaldehyde resin or resorcinol formaldehyde resin, and the p-tert-alkylphenol formaldehyde resin may be any one selected from the group consisting of p-tert-butylphenol formaldehyde resin, p-tert-octyl phenol formaldehyde resin, and a combination thereof.
- The adhesive may be included in an amount of 2 to 4 parts by weight with respect to 100 parts by weight of the raw rubber. Adhesion performance of the rubber may become disadvantageous when the adhesive is included in an amount of less than 2 parts by weight with respect to 100 parts by weight of the raw rubber, while physical properties of the rubber may be deteriorated when the adhesive is included in an amount of more than 4 parts by weight with respect to 100 parts by weight of the raw rubber.
- On the other hand, the tire according to the present disclosure may be a tire for a passenger vehicle, a tire for a racing car, an aircraft tire, a tire for an agricultural machine, a tire for off-the-road driving, a truck tire, a bus tire, or the like. Further, the tire may be a radial tire or a bias tire.
- Hereinafter, Examples of the present disclosure will be described in detail so that the present disclosure can be easily practiced by those skilled in the art to which the present disclosure pertains. However, the present disclosure can be implemented in various different forms and is not limited to the Examples described herein.
- Adhesive compositions were prepared by the same compositions as represented in the following Table 1. The following adhesive compositions do not comprise an organic solvent.
[Table 1] Composition Example 1 Example 2 Example 3 Example 4 Polybutadiene polyol (Weight average molecular weight: 2,800 g/mol) 95 92.5 95 90 Compound having a thiol group 2-mercaptoethanol 5 7.5 - - 2,2-(ethylenedioxy)diethanethiol - - 5 10 Tert-butyl perbenzoate 2 2 2 2 - Adhesive force values typical vulcanized synthetic rubbers used as materials for tire tread and polyurethane elastomers having a Shore A harness level of 95 were measured to measure adhesive force values according to adhesive compositions prepared in the Examples.
- First, after applying adhesive compositions having the above-mentioned compositions to the vulcanized synthetic rubbers in an amount of 0.001 g/in2, the adhesive compositions applied to the vulcanized synthetic rubbers were heat-treated at 110 °C for 30 minutes such that the vulcanized rubbers were sufficiently dipped in the adhesive compositions, and a thiol-ene click reaction was carried out.
- Subsequently, after applying a mixture of 1,4-butadiene and an ether-based polyurethane polymer having an isocyanate content of 8.5 wt% to the heat-treated adhesive compositions applied to the vulcanized synthetic rubbers, maintaining the mixture applied to the heat-treated adhesive compositions at 110 °C for 12 hours to cure the same, and measuring adhesive force values between polyurethane and the vulcanized rubbers, the measured adhesive force values are represented in the following Table 2.
[Table 2] Example 1 Example 2 Example 3 Example 4 T-peel adhesive force (kgf/cm) between polyurethane and vulcanized rubbers 11.72 12.06 11.87 13.21 - As can be confirmed in Table 2, it can be confirmed that high adhesive force values can be realized by an adhesive composition according to the present disclosure, and particularly bonding is perfectly made in the interface by seeing that breakage occurs in the vulcanized rubbers without an interface being broken when evaluating adhesive force values.
- Hereinabove, exemplary embodiments of the present disclosure have been described in detail. However, the scope of the present disclosure is not limited thereto, but various changes or modified forms of those skilled in the art using a basic concept of the present disclosure defined in the following claims can also be within the scope of the present disclosure.
Claims (6)
- A reactive solvent-free adhesive composition comprising:a polybutadiene polyol;a compound having a thiol group; anda radical initiator.
- The reactive solvent-free adhesive composition of claim 1, comprising 90 to 95 parts by weight of the polybutadiene polyol, 5 to 10 parts by weight of the compound having a thiol group, and 0.1 to 5 parts by weight of the radical initiator.
- The reactive solvent-free adhesive composition of claim 1, wherein the polybutadiene polyol is any one selected from the group consisting of cis-1,4-polybutadiene polyol, trans-1,4-polybutadiene polyol, 1,2-polybutadiene polyol, and hydroxyl-terminated polybutadiene, or mixtures of two or more thereof.
- The reactive solvent-free adhesive composition of claim 1, wherein the compound having a thiol group is an aliphatic thiol compound or an aromatic thiol compound.
- The reactive solvent-free adhesive composition of claim 1, wherein the radical initiator is any one selected from the group consisting of a photoinitiator, a peroxide initiator, and an azo compound, or mixtures of two or more thereof.
- A method of manufacturing a tire, the method comprising:a step (S1) of applying an adhesive composition to the surface of a vulcanized rubber for tire tread;a step (S2) of forming a polyurethane prepolymer on the adhesive composition; anda step (S3) of heating a resulting product of the step (S2), wherein the adhesive composition is a reactive solvent-free adhesive composition of any one of claims 1 to 5.
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EP (1) | EP3689636B1 (en) |
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US20140187697A1 (en) * | 2012-12-28 | 2014-07-03 | Hyundai Motor Company | Adhesives for bonding polyurethane and vulcanized rubber |
WO2018028365A1 (en) * | 2016-08-09 | 2018-02-15 | 翁秋梅 | Dynamic polymer with hybrid cross-linked network and application thereof |
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US6777026B2 (en) * | 2002-10-07 | 2004-08-17 | Lord Corporation | Flexible emissive coatings for elastomer substrates |
JP2004250647A (en) * | 2003-02-21 | 2004-09-09 | Mitsui Takeda Chemicals Inc | Adhesive composition and laminate using it |
FR2872820B1 (en) * | 2004-07-07 | 2008-09-05 | Conception & Dev Michelin Sa | ADHESIVE SYSTEM FOR THE DIRECT COLLECTION OF A POLYURETHANE COOKED WITH RAW RUBBER |
JP2011111563A (en) * | 2009-11-27 | 2011-06-09 | Toyoda Gosei Co Ltd | Adhesive, rubber hose equipped with reinforcing thread and method of manufacturing rubber hose |
CN103975033B (en) * | 2011-12-07 | 2016-04-13 | 第一毛织株式会社 | Photocurable adhesive composition and comprise its display unit |
JP6429797B2 (en) * | 2013-12-24 | 2018-11-28 | 株式会社ブリヂストン | Composition, adhesive and laminate |
EP3305547B1 (en) * | 2015-05-28 | 2019-07-24 | Bridgestone Corporation | Tire and method for producing same |
JP6452549B2 (en) * | 2015-05-28 | 2019-01-16 | 株式会社ブリヂストン | Tire and manufacturing method thereof |
JP7089589B2 (en) * | 2017-10-31 | 2022-06-22 | アルケマ フランス | Curable composition containing a thiol compound |
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US20140187697A1 (en) * | 2012-12-28 | 2014-07-03 | Hyundai Motor Company | Adhesives for bonding polyurethane and vulcanized rubber |
WO2018028365A1 (en) * | 2016-08-09 | 2018-02-15 | 翁秋梅 | Dynamic polymer with hybrid cross-linked network and application thereof |
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JP6810236B2 (en) | 2021-01-06 |
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